Photosynthesis of Urea by Cooperative Radicals Addition Using a Peptide as a Photocatalyst

Innovative strategies for efficient photocatalytic urea production are desirable due to the wide applications of urea and derivatives in agriculture and pharmaceuticals, which remain highly challenging. Here, we introduce a simple but efficient radical addition approach to address this challenge by fully utilizing the in situ, synchronously generated aminyl radical (·NH₂) and hydroperoxyl radical (HO₂·) via the coupling of photocatalytic NH₃ oxidation and O₂ reduction. The two radicals reassembled and cooperatively reacted with NH₂COOH to form urea with markedly lower kinetic barrier than the industrial process. This approach not only achieved record-high urea production and conversion rates (42.6 mmol g_cat ^-1 h^-1 and 70%, respectively) but also enabled the direct, single-step synthesis of unsymmetrical urea derivatives with good yields.